Hydrotreating catalyst with a titanium containing carrier and sulfur containing organic additive

ABSTRACT

Generally, it is disclosed a catalyst for use in a hydrotreating hydrocarbon feedstocks and the method of making such catalyst. It is generically provided that the catalyst comprises at least one Group VIB metal component, at least one Group VIII metal component, about 1 to about 30 wt % C, and preferably about 1 to about 20 wt % C, and more preferably about 5 to about 15 wt % C of one or more sulfur containing organic additive and a titanium-containing carrier component, wherein the amount of the titanium component is in the range of about 3 to about 60 wt %, expressed as an oxide (TiO2) and based on the total weight of the catalyst. The titanium-containing carrier is formed by co-extruding or precipitating a titanium source with a Al2O3 precursor to form a porous support material comprising Al2O3 or by impregnating a titanium source onto a porous support material comprising Al2O3.

REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.16/631,925, filed on Jan. 17, 2020, which is the National Stage Entry ofInternational Patent Application No. PCT/EP2018/069775, filed on Jul.20, 2018, which in turn claims the benefit of U.S. Provisional PatentApplication No. 62/535,610 filed on Jul. 21, 2017, the disclosures ofwhich are incorporated herein by reference.

TECHNICAL FIELD

The present invention is in the field of catalysts useful forhydrotreating hydrocarbon feedstocks in refining processes.

THE INVENTION

In general, hydrotreating catalysts are composed of a carrier havingdeposited thereon a Group VIB (of the Periodic Table) metal componentand a Group VIII (of the Periodic Table) metal component. The mostcommonly employed Group VIB metals are molybdenum and tungsten, whilecobalt and nickel are the conventional Group VIII metals. Phosphorus mayalso be present in the catalyst. The prior art processes for preparingthese catalysts are characterized in that a carrier material iscomposited with hydrogenation or hydrotreating metal components, forexample by impregnation, after which the composite is generally calcinedto convert the metal components into their oxides. Before being used inhydrotreating, the catalysts are generally sulfided to convert thehydrogenation metals into their sulfides. Processes for activating andregenerating such catalysts are also known.

The use of TiO₂-containing carriers in hydroprocessing catalysts, whichare generally calcined after application of the active metals, is widelyknown. The inclusion of TiO₂ in the hydroprocessing carriers hascommonly been reported to show higher desulfurization activity, but thefundamentals behind such behavior are not well understood. For example,US Patent Publications US20120181219 and US20130153467 disclose a metalcomponent selected from Groups VIA and VIII in the periodic table,supported on a silica-titania-alumina support where the total of thediffraction peak area indicating the crystal structure of anatasetitania (101) planes and the diffraction peak area indicating thecrystal structure of rutile titania (110) planes is ¼ or less of thediffraction peak area indicating the aluminum crystal structure ascribedto γ-alumina (400) planes, as measured by X-ray diffraction analysis.However, these references fail to disclose the combination of thepresent invention, (i.e. the combination of a TiO₂ containing supportand the use of sulfur containing organic additive).

Another example is U.S. Pat. No. 6,383,975 which discloses a catalystthat uses a support consisting on an alumina matrix, having dispersed onits surface or in its mass, or in both, a metal oxide from group IVB ofthe periodic table. The support is prepared by co-precipitationtechnique, co-gelification or impregnation of the alumina with a Ticompound, soluble in an organic solvent, followed by drying at 100 to200° C. and calcination at 400 to 600° C., on oxidizing atmosphere.However, this reference also fails to disclose the combination of thepresent invention as it does not disclose the synergistic effect oftitanium and sulfur organic additives.

Another example is U.S. Pat. No. 9,463,452 which discloses a catalystthat uses a titania coated alumina particles shaped into extrudates. Thehydrotreating catalyst then supports a periodic table group 6 metalcompound, a periodic table group 8-10 metal compound, a phosphoruscompound, and a saccharide. The invention of the '452 patent is limitedto a very specific manufacturing process and only to the use ofsaccharides as potential additives.

It was found that by using TiO₂-containing carriers in combination withthe use of certain sulfur containing organics in the preparation method,highly active hydrotreating catalysts can be made. The activity of thesecatalysts is higher than (i) what can be achieved on a conventionalAl₂O₃ support with the same organic or (ii) when the TiO₂-containingcatalysts are being prepared without sulfur containing organics.Moreover, it appears the activity of the active phase in the catalystprepared with TiO₂-containing supports in combination with sulfurcontaining organics is higher than can be expected based on the effectof the individual contributions of these parameters. This higher activephase activity can be applied to generate hydrotreating catalysts with asuperior volumetric activity or catalysts with high activity atconsiderably lower concentrations of the active Group VIB and Group VIIImetal components.

Thus, in one embodiment of the invention there is provided a catalystcomprising at least one Group VIB metal component, at least one GroupVIII metal component, about 1 to about 30 wt % C, and preferably about 1to about 20 wt % C, and more preferably about 5 to about 15 wt % C ofone or more sulfur containing organic additive and a titanium-containingcarrier component, wherein the amount of the titanium component is inthe range of about 3 to about 60 wt %, expressed as an oxide (TiO₂) andbased on the total weight of the catalyst. The titanium-containingcarrier is formed by co-extruding or precipitating a titanium sourcewith a Al₂O₃ precursor to form a porous support material comprisingAl₂O₃ or by impregnating a titanium source onto a porous supportmaterial comprising Al₂O₃.

In another embodiment of the invention, provided is a method ofproducing a catalyst. The method comprises the preparation of aTi-containing porous support material comprising Al₂O₃. This can beachieved by co-extruding or precipitating a titanium source with a Al₂O₃precursor, shaping to form carrier extrudates, followed by drying andcalcination. Alternatively, porous Al₂O₃ extrudates may be impregnatedwith a Ti-source followed by drying and calcination. The Ti-containingporous support is impregnated with a solution comprised of at least oneGroup VIB metal source and/or at least one Group VIII metal source. Oneor more sulfur containing organic additive is added in the productionprocess either by co-impregnation with the metal sources or via apost-impregnation. In the process, the amount of the titanium source issufficient so as to form a catalyst composition at least having atitanium content in the range of about 3 wt % to about 60 wt %,expressed as an oxide (TiO₂) and based on the total weight of thecatalyst after calcination.

In another embodiment of the invention, there is provided a catalystcomposition formed by the just above-described process. Anotherembodiment of the invention is a hydrotreating process carried outemploying the catalyst composition.

These and still other embodiments, advantages and features of thepresent invention shall become further apparent from the followingdetailed description, including the appended claims.

FURTHER DETAILED DESCRIPTION OF THE INVENTION

Unless otherwise indicated, weight percent (wt. %) as used herein is theweight percent of the specified form of the substance, based upon thetotal weight of the product for which the specified substance or form ofsubstance is a constituent or component. The weight percent of TiO₂ andGroup VIB and Group VIII metals-oxides are based on the total weight ofthe final catalyst after calcination, i.e. excluding the presence oforganics and/or water. The weight percent of organics in the finalcatalyst is based on the total weight of the final catalyst withoutcalcination. It should further be understood that, when describing stepsor components or elements as being preferred in some manner herein, theyare preferred as of the initial date of this disclosure, and that suchpreference(s) could of course vary depending upon a given circumstanceor future development in the art.

The Group VIB metal component in catalysts of the invention is selectedfrom the group consisting of molybdenum, tungsten, chromium and amixture of two or more of the foregoing, while molybdenum and/ortungsten is typically preferred, and molybdenum is typically morepreferred. The Group VIII metal component is selected from groupconsisting of iron, cobalt and nickel, while nickel and/or cobalt aretypically preferred. Preferred mixtures of metals include a combinationof (a) nickel and/or cobalt and (b) molybdenum and/or tungsten. Whenhydrodesulfurization (sometimes hereafter referred to as “HDS”) activityof the catalyst is important, a combination of cobalt and molybdenum isadvantageous and typically preferred. When hydrodenitrogenation(sometimes hereafter referred to as “HDN”) activity of the catalyst isimportant, a combination of nickel and either molybdenum or tungsten isadvantageous and typically preferred.

The Group VIB metal component can be introduced as an oxide, an oxoacid, or an ammonium salt of an oxo or polyoxo anion. The Group VIBmetal compounds are formally in the +6 oxidation state. Oxides and oxoacids are preferred Group VIB metal compounds. Suitable Group VIB metalcompounds in the practice of this invention include chromium trioxide,chromic acid, ammonium chromate, ammonium dichromate, molybdenumtrioxide, molybdic acid, ammonium molybdate, ammonium para-molybdate,tungsten trioxide, tungstic acid, ammonium tungsten oxide, ammoniummetatungstate hydrate, ammonium para-tungstate, and the like. PreferredGroup VIB metal compounds include molybdenum trioxide, molybdic acid,tungstic acid and tungsten trioxide. Mixtures of any two or more GroupVIB metal compounds can be used; a mixture of products will be obtainedwhen compounds having different Group VIB metal are used. The amount ofGroup VIB metal compound employed in the catalyst will typically be inthe range of about 15 to about 30 wt % (as trioxide), based on the totalweight of the catalyst.

The Group VIII metal component is usually introduced as an oxide,hydroxide or salt. Suitable Group VIII metal compounds include, but arenot limited to, cobalt oxide, cobalt hydroxide, cobalt nitrate, cobaltcarbonate, cobalt hydroxy-carbonate, cobalt acetate, cobalt citrate,nickel oxide, nickel hydroxide, nickel nitrate, nickel carbonate, nickelhydroxy-carbonate, nickel acetate, and nickel citrate. Preferred GroupVIII metal compounds include cobalt carbonate, cobalt hydroxy-carbonate,cobalt hydroxide, nickel hydroxy-carbonate nickel carbonate and nickelhydroxide. Mixtures of two or more Group VIII metal compounds can beused; when the Group VIII metals of the compounds in the mixture aredifferent, a mixture of products will be obtained. The amount of GroupVIII metal compound employed in the catalyst will typically be in therange of about 2 to about 8 wt % (as oxide), based on the total weightof the catalyst. In a preferred embodiment of this invention, the amountof Group VIII metal compound is in the range of about 2 to about 6 wt %(as oxide), based on the total weight of the catalyst.

The titanium component will typically be introduced as titania, titanylsulfate, titanium sulfate, Titanium(IV)bis(ammonium lactato)dihydroxide,titanium alkoxide (like Ti-isopropoxide, Ti-butoxide, Ti-ethoxide,etc.), or TiCl₄. The amount of the titanium component in the catalystwill typically be in the range of about 3 to about 60 wt %, expressed asan oxide (TiO₂) and based on the total weight of the catalyst. In apreferred embodiment of this invention, the amount of titanium componentis in the range of about 5 wt % to about 50 wt %, expressed as an oxide(TiO₂) and based on the total weight of the catalyst.

The catalyst carrier may further comprise the conventional oxides, e.g.,alumina, silica, silica-alumina, alumina with silica-alumina dispersedtherein, silica-coated alumina, alumina-coated silica. As a rule,preference is given to the carrier being of alumina, silica-alumina,alumina with silica-alumina dispersed therein, alumina-coated silica orsilica-coated alumina. Special preference is given to alumina andalumina containing up to 5 wt % of silica. The silicon component used inthe preparation of the support will typically be sodium silicate(waterglass) or silicon dioxide. The combining of the silicon sourcewith the alumina source may be carried out, e.g., by co-precipitation,kneading (co-extrusion), immersion, impregnation, etc. Preferably, thesilicon source is introduced in the precipitation step. For theincorporation, the silicon compound can also be dispersed in a solventif need be. A carrier containing a transition alumina, for example aneta, theta, or gamma alumina is preferred within this group, wherein agamma-alumina carrier is most especially preferred.

The physical properties of the final carrier are not critical to theprocess according to the invention, since the synergistic effect betweenthe use of titania containing carriers and sulfur containing organicsshould be always observed. However, it is known that there is a specificrange of pore size, surface area and pore volume that performs betterdepending on the hydroprocessing application. All physical propertiesare measured via nitrogen physisorption techniques (Quadrasorb equipmentand 300° C. pretreatment overnight under vacuum).

The carrier's pore volume (measured at 100 nm assuming de Boer andKelvin equations to convert relative pressure into pore diameter), willgenerally be in the range of 0.2 to 2 ml/g, preferably 0.4 to 1 ml/g.The carrier specific surface area will generally be in the range of 50to 400 m²/g (measured using the BET method). Preferably, the carrierwill have a median pore diameter in the range of 5 to 15 nm.

The catalyst is employed in the conventional manner in the form of, forexample, spheres or extrudates. Examples of suitable types of extrudateshave been disclosed in the literature (see, int. al., U.S. Pat. No.4,028,227).

The titanium compound can be incorporated into the carrier byimpregnation, co-extrusion or precipitation, atomic layer deposition(ALD), or chemical vapor deposition (CVD). It is preferred that thetitanium component is precipitated with the other components of thecarrier, as it is believed, without being bound to theory, thatprecipitation results in a better dispersion of the titanium componentemployed in the highly active catalyst of this invention than what canbe achieved via co-extrusion. Furthermore, the addition of the titaniumcomponent in this step prevents the need for an additional productionstep, as is the case when impregnation, ALD or CVD are used.

When adding the titanium via co-precipitation, known methods ofco-precipitation can be used. In particular, Aluminum sulfate (Alum) andTitanyl sulfate (TiOSO₄) or titanium sulfate can be mixed in one streamand sodium aluminate (Natal) are dosed either simultaneously orsubsequently to a heel of water at elevated T and a pH>7. Thecompositions and flow rates of Natal and Alum/TiOSO₄/titanium sulfatecan be adjusted to achieve the desired final TiO₂ content in the thuscreated TiO₂/Al₂O₃ material. The pH can be controlled constantly withNaOH or H₂SO₄. Total dosing time can be varied between 10 min and 2hours and the final solid concentration in the reactor will beapproximately 2-10% on weight basis. In a subsequent step, the pH can beraised with NaOH or Natal to 9-12 to age. The slurry is then filteredand washed. The obtained solid can then be shaped into support bodiesvia extrusion, pelletizing or pressing which can be preceded by drying,spray-drying, milling, kneading and other methods known in the art toarrive at an extrudable material.

Strike-precipitation is very similar to co-precipitation processes, butthe acidic stream is added to the basic components dispersed in thereactor vessel. Natal is diluted in water and under vigorous stirringwaterglass is added while heating at 60° C. To this mixture aluminumsulfate and titanyl sulfate are added in 20 min with a final pH of 6.5.pH is not controlled during the addition and only allow to settle withthe complete dossing of both streams. NaOH is used to adjust the pH to7.2 and the mixture is aged for 1 hour at 60° C. while stirring. Thecake is re-slurried with water, brought to pH 10 with ammonia and agedat 95° C. for 1 hour while stirring. Then, the slurry is filtered andwashed with water to remove excess ammonia. The obtained solid can thenbe shaped into support bodies via extrusion, pelletizing or pressingwhich can be preceded by drying, spray-drying, milling, kneading andother methods known in the art to arrive at an extrudable material.

Step-precipitation can be carried out by reaction or precipitation of aTi-precursor such as titanyl sulfate on a slurry of boehmite orpseudo-boehmite in water. Firstly alumina is precipitated viasimultaneous dosing of sodium aluminate (Natal) and aluminum sulfate(Alum) to a heel of water at elevated T and a pH>7. The flows of Nataland Alum can be adjusted and the pH is controlled with NaOH or H₂SO₄.After aging at pH 9-12, filtration and washing, the thus-formed boehmiteor pseudo-boehmite filter cake is re-slurried in water. To this slurryTiOSO₄ or titanium sulfate can be added either simultaneously orsubsequently with NaOH at elevated T and pH>7 in about 10 minutes to 1hour. The slurry is then filtered and washed. The thus thus-obtainedsolid can then be shaped into support bodies via extrusion pelletizingor pressing, which can be preceded by drying, spray-drying, milling,kneading and other methods known in the art to arrive at an extrudablematerial.

Co-extrusion is carried out by adding the titanium component to analumina precursor component during a kneading or mixing step. The momentof addition is not fixed. The titanium component is added as a solid oras a solution. During the kneading or mixing step, the mix is heated toa desired temperature to remove any excess of solvent/water if needed.Kneading or mixing is finished when the desired moisture content (asdetermined by Loss on Ignition at a temperature in the range of 500-600°C.) is reached. Next, the mix is shaped to extrudates by using asuitable shaping technique. Besides extrusion, shaping can beaccomplished via pelletizing or pressing.

The support bodies formed via precipitation and co-extrusion methods arethen dried at a temperature in the range of 80-200° C. to remove asubstantial amount of solvent/water and then calcined under air or inertconditions with or without steam at a temperature in the range of400-900° C., resulting in the case of alumina, in a carrier containing atransition alumina e.g., a gamma, theta or eta-alumina. The titaniacomponent will also be present as an oxide, such as anatase or rutile.The calcination can be in a static or rotating mode.

When adding the titanium via impregnation, the titanium precursor isapplied to a porous carrier, comprising Al₂O₃. Known methods ofimpregnation can be used. In particular, pore volume impregnation ispreferred. A solution of aqueous titantia precursor, such as titanylsulfate, titanium sulfate or Titanium(IV)bis(ammoniumlactato)dihydroxide is prepared. Alternatively, a non-aqueous solutionof an alkoxide titantia can be prepared. Then, the alumina extrudate iscoated/impregnated with the titanium solution. The impregnated carrierso formed is then dried at a temperature in the range of 80-200° C. toremove a substantial amount of solvent/water and then generally calcinedunder air or inert conditions with or without steam at a temperature inthe range of 400-700° C.

In preparation of the TiO₂ containing support material it may beadvantageous that part of the TiO₂ is introduced in one step, whileanother part of the TiO₂ is introduced in another step.

The calcined extrudates comprising Al₂O₃ and TiO₂ are then impregnatedwith a solution comprising a Group VIB metal source and/or a Group VIIImetal source and optionally a phosphorous source. Impregnation iscarried out by pore volume impregnation with an impregnation solutionthat can also comprise the selected sulfur containing organic additivesin an appropriate solvent. The solvent used in preparing the additiveimpregnation solution is generally water, although other components suchas methanol, ethanol and other alcohols may also be suitable.Impregnation can be carried out at room temperature or at elevatedtemperatures, but will typically be carried out at about 20-100° C.Instead of impregnating techniques, dipping methods, spraying methods,etc. can be used. After impregnation, an optional drying step is carriedout with the objective to remove water, but leave (the largest part) ofthe organic additive on the catalyst. Drying is typically carried out ata temperature in the range of 25-220° C., although higher T, shortcontact time drying may also be applied. In case the sulfur containingorganics are not added in the impregnation solution containing themetal-precursors, a subsequent impregnation step is carried out.

The final catalyst further comprises one or more sulfur containingorganic additive. The one or more sulfur containing organic additive isadded in amount of about 1 to about 30 wt % C, and preferably about 1 toabout 20 wt % C, and more preferably about 5 to about 15 wt % C byweight of the final catalyst. This organic additive can be addedtogether with the Group VIB metal source and/or a Group VIII metalsource or in a separate step. The sulfur containing organic compoundpreferably is selected from the group of compounds comprising amercapto-carboxylic acid of formula HS—R—COOH, where R is a linear orbranched, and saturated or unsaturated carbon backbone (C₁-C₁₁ with orwithout hetero atoms such as nitrogen) with optionally anitrogen-containing functional group such as amine, amide, etc. Suitableexamples of such mercapto-carboxylic acid include, but are not limitedto, thioglycolic acid, thiolactic acid, thiopropionic acid, mercaptosuccinic acid, and cysteine or mixtures thereof.

The metals, additional phosphorus, and the sulfur containing organicadditives can be introduced onto the extrudates in one or more steps.The solutions used may or may not be heated.

For the one step approach, a solution containing at least one Group VIBmetal source, at least one Group VIII metal source along with aphosphorus source in various ratios is prepared, typically using wateras the solvent. Other carboxylic acids, such as citric acid, malonicacid, gluconic acid, adipic acid, and malic acid may be added. Theresulting solution can be acidic and have a pH in the range of 0-7. Anadditional amount of the mercapto-carboxylic acid may be also added in asubsequent step. The said solution, either heated or as such, isintroduced onto the support extrudates over a time period of 2-60minutes (depending on the total amount and metal content of thecatalyst) staying close to but not necessarily reaching the saturationof its pore volume. After impregnation the catalyst is allowed to ageuntil free flowing extrudates are obtained and further aged between60-160° C., preferably between 80-120° C. In case of using higheramounts of additives that correspond to an additive/metal ratio of aboveabout 0.5 equivalents of the sulfur amount necessary for forming MoS₂,WS₂, CoS and/or NiS, the resulting solution might be too viscous toimpregnate. Additionally, precipitation of metals/additive should beavoided. In the event of precipitation, it is not advised to filter offthe precipitate to have an impregnable solution and to furtherimpregnate this filtered solution. Viscous solutions or solutions withprecipitates should be avoided by various methods known in the art. Oneapproach could be further dilution with water (or another appropriatesolvent), possibly reaching volumes much higher than the available porevolume of the support. In such a case, the solution can be added in twoor more steps, with drying steps in between. Heating the solution isanother common method, though excess heating in air might result in aneven more viscous solution. As such, cooling or handling the solution inan inert atmosphere is considered a viable approach. The final preparedcatalyst is eventually subjected to a final ageing step between 60 and160° C., preferably between 80 and 120° C. The ageing is normallyperformed in air. Optionally, ageing the catalysts in an inertatmosphere could be helpful to improve physical properties (such asavoid inter-extrudate lumping) but is not crucial for the invention.Prior to the activation (pre-sulfidation) and catalytic testing, acalcination treatment at temperatures above the activation and testtemperature, especially if it leads to oxidation of the sulfurcomponent, is not preferred, because it might hamper the catalyticactivity. Furthermore, any other treatment that leads to the oxidationof the sulfur component is also to be avoided.

For the multiple step approach, metals are first introduced onto thesupport and the mercapto-carboxylic acid additive is introducedsubsequently. The metal solution may or may not be heated. The supportextrudates are impregnated with a solution containing at least one GroupVIB metal source, at least one Group VIII metal source along with aphosphorus source in various ratios. Other carboxylic acids, such ascitric acid and those mentioned above may be added, either as part ofthe metal solution or in subsequent steps. Water is typically used asthe solvent for preparation of the impregnation solution, while it isbelieved other solvents known in the art can be used. The resultingsolution can be acidic and have a pH in the range of 0 and 7. The saidsolution is introduced onto the extrudates using 90 to 120% saturationof its pores. During the mixing/impregnation process, the catalyst isallowed to age whilst rotating to enable even mixing of all thecomponents. The impregnated material is further dried between 80 to 150°C., preferably between 100 to 120° C., until the excess of water isremoved and ‘free flowing’ catalyst extrudates are obtained. Theresulting catalyst can have a moisture content in the range of 0 to 20%.Optionally, the impregnated extrudates can be calcined at temperaturesup to (for example) 600° C. The mercapto-carboxylic acid is thencarefully added as droplets or a continuous stream to the resultingcatalysts (as a neat liquid or as a mixture with water or anotherappropriate solvent) over a time period of typically 2 to 60 minutesdepending on the total amount of catalyst and metal content thereof. Theimpregnated catalyst is allowed to age until free flowing extrudates areobtained. The catalyst is then subjected to a final ageing/heattreatment step (in air or under inert atmosphere) between 60 and 160°C., preferably between 80 and 120° C. The ageing is normally performedin air. Optionally ageing the catalysts in an inert atmosphere could behelpful to improve physical properties (such as to avoid inter-extrudatelumping) but is not crucial for the invention. Prior to the activation(pre-sulfidation) and catalytic testing, a calcination treatment attemperatures above the activation and test temperature, especially if itleads to oxidation of the sulfur component, is not preferred, because itmight hamper the catalytic activity. Furthermore, any other treatmentthat leads to the oxidation of the sulfur component is also to beavoided.

In the practice of this invention, the impregnation solution mayoptionally include a phosphorus component. The phosphorous component isa compound which is typically a water soluble, acidic phosphoruscompound, particularly an oxygenated inorganic phosphorus-containingacid. Examples of suitable phosphorus compounds include metaphosphoricacid, pyrophosphoric acid, phosphorous acid, orthophosphoric acid,triphosphoric acid, tetraphosphoric acid, and precursors of acids ofphosphorus, such as ammonium hydrogen phosphates (mono-ammoniumdi-hydrogen phosphate, di-ammonium mono-hydrogen phosphate, tri-ammoniumphosphate). Mixtures of two or more phosphorus compounds can be used.The phosphorus compound may be used in liquid or solid form. A preferredphosphorus compound is orthophosphoric acid (H₃PO₄) or an ammoniumhydrogen phosphate, preferably in aqueous solution. The amount ofphosphorus compound employed in the catalyst will preferably be at leastabout 1 wt % (as oxide P₂O₅), based on the total weight of the catalystand more preferably in the range of about 1 to about 8 wt % (as oxideP₂O₅), based on the total weight of the catalyst.

Optionally, catalysts of the invention may be subjected to a sulfidationstep (treatment) to convert the metal components to their sulfides. Inthe context of the present specification, the phrases “sulfiding step”and “sulfidation step” are meant to include any process step in which asulfur-containing compound is added to the catalyst composition and inwhich at least a portion of the hydrogenation metal components presentin the catalyst is converted into the sulfidic form, either directly orafter an activation treatment with hydrogen. Suitable sulfidationprocesses are known in the art. The sulfidation step can take place exsitu to the reactor in which the catalyst is to be used in hydrotreatinghydrocarbon feeds, in situ, or in a combination of ex situ and in situto the reactor.

Ex situ sulfidation processes take place outside the reactor in whichthe catalyst is to be used in hydrotreating hydrocarbon feeds. In such aprocess, the catalyst is contacted with a sulfur compound, e.g., apolysulfide or elemental sulfur, outside the reactor and, if necessary,dried. In a second step, the material is treated with hydrogen gas atelevated temperature in the reactor, optionally in the presence of afeed, to activate the catalyst, i.e., to bring the catalyst into thesulfided state.

In situ sulfidation processes take place in the reactor in which thecatalyst is to be used in hydrotreating hydrocarbon feeds. Here, thecatalyst is contacted in the reactor at elevated temperature with ahydrogen gas stream mixed with a sulfiding agent, such as hydrogensulfide or a compound which under the prevailing conditions isdecomposable into hydrogen sulfide. It is also possible to use ahydrogen gas stream combined with a hydrocarbon feed comprising a sulfurcompound which under the prevailing conditions is decomposable intohydrogen sulfide. In the latter case, it is possible to sulfide thecatalyst by contacting it with a hydrocarbon feed comprising an addedsulfiding agent (spiked hydrocarbon feed), and it is also possible touse a sulfur-containing hydrocarbon feed without any added sulfidingagent, since the sulfur components present in the feed will be convertedinto hydrogen sulfide in the presence of the catalyst. Combinations ofthe various sulfiding techniques may also be applied. The use of aspiked hydrocarbon feed may be preferred.

Apart from the activity benefit of these mercapto-carboxylic acids; theuse of mercapto-carboxylic acids is beneficial because of the sulfidingproperties of the final catalyst: due to the sulfur present in thecompound, catalyst sulfidation is (in part) reached by the sulfur fromthe catalyst itself. This opens up possibilities for DMDS-lean (or feedonly) or even hydrogen-only start-ups. In the context of the presentspecification, the phrases “sulfiding step” and/or “sulfidation step”and/or “activation step” are meant to include any process step in whichat least a portion (or all) of the hydrogenation metal componentspresent in the catalyst is converted into the (active) sulfidic form,usually after an activation treatment with hydrogen and optionally inthe additional presence of a feed and/or (sulfur rich) spiking agent.Suitable sulfidation or activation processes are known in the art. Thesulfidation step can take place ex situ to the reactor in which thecatalyst is to be used in hydrotreating hydrocarbon feeds, in situ, orin a combination of ex situ and in situ to the reactor.

Regardless of the approach (ex situ vs in situ), catalysts described inthis invention can be activated using the conventional start-uptechniques known in the art. Typically, the catalyst is contacted in thereactor at elevated temperature with a hydrogen gas stream mixed with asulfiding agent, such as hydrogen sulfide or a compound which under theprevailing conditions is decomposable into hydrogen sulfide. It is alsopossible to use a sulfur-containing hydrocarbon feed, without any addedsulfiding agent, since the sulfur components present in the feed will beconverted into hydrogen sulfide in the presence of the catalyst.

The catalyst compositions of this invention are those produced by theabove-described process, whether or not the process included an optionalsulfiding step.

The formed catalyst product of this invention is suitable for use inhydrotreating, hydrodenitrogenation and/or hydrodesulfurization (alsocollectively referred to herein as “hydrotreating”) of hydrocarbon feedstocks when contacted by the catalyst under hydrotreating conditions.Such hydrotreating conditions are temperatures in the range of 250-450°C., pressure in the range of 5-250 bar, liquid space velocities in therange of 0.1-10 liter/hour and hydrogen/oil ratios in the range of50-2000 NUL Examples of suitable hydrocarbon feeds to be so treated varywidely, and include middle distillates, kero, naphtha, vacuum gas oils,heavy gas oils, and the like.

The following describes experimental preparation of the support and thecatalyst, as well as use of the catalyst in hydrotreating a hydrocarbonfeedstock to illustrate activity of the catalysts so formed. Thisinformation is illustrative only, and is not intend to limit theinvention in any way.

EXAMPLES Activity Test

The activity tests were carried out in micro flow reactors. Light GasOil (LGO) spiked with dimethyl disulfide (DMDS) (total S content of 2.5wt %) was used for presulfiding, A Straight-run Gas Oil (SRGO), having aS content of 1.4-1.1 wt. % and a N content of 215-200 ppm, was used fortesting in examples A-E. A VGO having a S content of 2.1 wt % and a Ncontent of 1760 ppm N was used in example F. Testing takes place atequal volumetric catalyst intake. The relative volumetric activities forthe various catalysts were determined as follows. For each catalyst thevolumetric reaction constant kw,′ was calculated using n^(th) orderkinetics and a reaction order of 1.0 for HDN and 1.2 for HDS. Therelative volumetric activities (RVA) of the different catalysts of theinvention vs a comparative catalyst were subsequently calculated bytaking the ratio of the reaction constants.

In the tables, SA is surface area, PV is pore volume, DMPD is mean porediameter based on the desorption branch of the N₂ physisorption isother,S is sulfur, N is nitrogen, P is pressure, goat is the amount ofcatalyst in the reactor, LHSV is liquid hourly space velocity, and r.o.is reaction order.

Support Preparation

The following supports were made in accordance with the proceduresdescribed below. One support was prepared as a reference (Si, Al₂O₃). Asummary of the properties for each support can be found in Table 1.

Example S1: Comparative S1. Comparative S1 was 100% standard Al₂O₃prepared via a co-precipitation process. Aluminum sulfate (Alum) andsodium aluminate (Natal) were dosed simultaneously to a heel of water at60° C. and pH 8.5. The flows of Natal and Alum were fixed and the pH wascontrolled constantly with NaOH or H₂SO₄. Total dosing time wasapproximately 1 hour and the final Al₂O₃ concentration in the reactorwas approximately 4% on weight basis. The pH was then raised with NaOHor Natal to approximately 10 and the slurry was aged for 10 minuteswhile stirring. The slurry was filtered over a filter cloth and washedwith water or a solution of ammonium bi-carbonate in water untilsufficient removal of sodium and sulfate. The cake was dried, extrudedand calcined.

Example S2: Support S2. The support S2 was prepared via a co-extrusionprocess of alumina and titania filter cakes. The alumina filter cake wasprepared via the process described in Example S1 (prior extrusion). Thetitania filter cake was prepared via hydrolysis of an aqueous solutionof TiOSO₄ at 99° C. for 5 hours followed by neutralization with NaOH topH 7. The precipitate was filtered and washed salt free using water or aammonium bi-carbonate solution. The two filter cakes were mixed in akneader and extruded. The extrudates were calcined at 650° C. for 1 hourunder airflow of ca. 10 nL/min. The final composition of the support(dry base) was found to be 49.7 wt. % TiO₂ and 50.3 wt. % Al₂O₃.

Example S3: Support S3. The support S3 was prepared via aco-precipitation process. Aluminum sulfate (Alum) and Titanyl sulfate(TiOSO₄) mixed in one stream and sodium aluminate (Natal) were dosedsimultaneously to a heel of water at 60° C. and pH 8.5. The flows ofNatal and Alum/TiOSO₄ were fixed and the pH was controlled constantlywith NaOH or H₂SO₄. Total dosing time was approximately 1 hour and thefinal solid concentration in the reactor was approximately 4% on weightbasis. The pH was then raised with NaOH or Natal to approximately 10 andthe slurry was aged for 20 minutes while stirring. The slurry wasfiltered over a filter cloth and washed with water or a solution ofammonium bi-carbonate in water until sufficient removal of sodium andsulfate. The cake was dried, extruded and calcined at 650° C. for 1 hourunder airflow of ca. 10 nL/min. The final composition of the support(dry base) was found to be 48.0 wt. % TiO₂ and 52.0 wt. % Al₂O₃.

Example S4: Support S4. The support S4 was prepared by co-precipitationusing the same process as was used to prepare support S3, but usingdifferent amounts of the TiO₂ and Al₂O₃ precursors. The finalcomposition of the support (dry base) was found to be 20.9 wt. % TiO₂and 79.1 wt. % Al₂O₃.

Example S5: Support S5. The support S5 was prepared by consecutive(Step-) precipitation of alumina and titania. Firstly alumina (boehmite)was precipitated according to the procedure as described in 51. Afterfiltration and proper washing, the precipitate was transferred back tothe reactor. Boehmite filter cake was slurried in a stainless steelvessel with water and stirred while heating up to 60° C. To the slurryTiOSO₄ solution was dosed at a fixed rate and the pH was controlled at8.5 via addition of NaOH solution. The dosing time was 25 minutes at 60°C. The slurry was thoroughly washed with water or a solution of ammoniumbi-carbonate in water to remove salts, dried, extruded and calcined at650° C. for 1 hour under airflow of ca. 10 nL/min. The final compositionof the support (dry base) was found to be 21.1 wt. % TiO₂ and 78.9 wt. %Al₂O₃.

Example S6: Support S6. The support S6 was prepared by coating anaqueous titania precursor on alumina extrudates. The extrudates usedconsisted predominantly of γ-alumina and had a surface area of 271 m²/g,a pore volume of 0.75 ml/g and a mean pore diameter of 8.7 nm asdetermined from the N₂ physisorption desorption isotherm. The pores ofthe alumina extrudates were filled with an aqueous solution ofTitanium(IV)bis(ammonium lactato)dihydroxide, aged for 2 hours at 60° C.and pre-dried in a rotating pan until the appearance of the extrudateswas no longer wet and eventually dried overnight at 120° C. The samplewas calcined at 450° C. for 2 hours under airflow. This procedure wasrepeated a second time reaching higher titania loadings. The finalcomposition of the support (dry base) was found to be 27.8 wt. % TiO₂and 72.2 wt. % Al₂O₃.

Example S7: Support S7. The support S7 was prepared by coating analkoxide titania precursor on alumina extrudates. The extrudates usedhad the same characteristics as those used in S6. The pores of thealumina were filled with Ti-isopropoxide solution in propanol. The agingprocess was carried out inside an atmosbag filled with a N₂ atmosphereat room temperature for 2 hours, and then the same was placed outside ofthe atmosbag for hydrolysis overnight (at RT). Finally the sample wasdried at 120° C. overnight and calcined at 450° C. for 2 hours. Thefinal composition of the support (dry base) was found to be 18.9 wt. %TiO₂ and 81.1 wt. % Al₂O₃.

Example S8: Support S8. The support S8 was prepared by a second coatingwith an alkoxide titania precursor on the TiO₂—Al₂O₃ extrudates obtainedin S7. The procedure as described in S7 was repeated a second timereaching higher titania loadings. The final composition of the support(dry base) was found to be 43.7 wt. % TiO₂ and 56.3 wt. % Al₂O₃.

Example S9: Support S9. The support S9 was prepared bystrike-precipitation of alumina and titania. Natal was diluted in waterand under vigorous stirring waterglass was added while heating at 60° C.To this mixture aluminum sulfate and titanyl sulfate were added in 20min with a final pH of 6.5. NaOH was used to adjust the pH to 7.2 andthe mixture was aged for 1 hour at 60° C. while stirring. The cake wasre-slurried with water, brought to pH 10 with ammonia and aged at 95° C.for 1 hour while stirring. Then, the slurry was filtered and washed withwater to remove excess ammonia, dried, extruded and calcined at 650° C.for 1 hour under airflow of ca. 10 nL/min with 25 vol. % steam. Thefinal composition of the support (dry base) was found to be 23.1 wt. %TiO₂, 3.2 wt. % SiO₂ and 73.7 wt. % Al₂O₃.

Example S10: Support S10. The support S10 was prepared in the same wayas S9, but similar TiO₂ and lower SiO₂ sources were used. The finalcomposition of the support (dry base) was found to be 21.3 wt. % TiO₂,0.5 wt. % SiO₂ and 78.2 wt. % Al₂O₃.

Example S11: Support S11. The support S11 was prepared in the same wayas S9, but lower TiO₂ and SiO₂ sources were used. The final compositionof the support (dry base) was found to be 10.8 wt. % TiO₂, 0.5 wt. %SiO₂ and 88.7 wt. % Al₂O₃.

Example S12: Support S12. The support S12 was prepared byco-extrusion/kneading of Al₂O₃ cake and a titanium source. TheTitanium(IV)isopropoxide (titania source) was added after 15 minuteskneading time. Later a vent hole was opened in order to let the alcoholevaporate. The kneaded material was extruded and then, the plate withwet extrudates was placed in the stove and kept there overnight at 120°C. Finally, the sample was calcined at 650° C. with 25% steam. The finalcomposition of the support (dry base) was found to be 10.6 wt. % TiO₂,0.87 wt. % SiO₂ and the rest is Al₂O₃.

The sodium content present is any of these supports is very low (<0.5wt. %), since it is known as detrimental for the hydroprocessingactivity. A summary of the compositions and characteristics of thesedifferent supports can be found in Table 1.

TABLE 1 Summary of supports prepared in Examples S1-12 and some of theirphysical properties. Weight % Weight % SA PV DMPD Support Procedure TiO₂(*) SiO2 (*) (m²/g) (ml/g) (nm) S1 reference 0 — 271 0.84 8.1 S2co-extrusion 47.9 — 200 0.52 8.7 S3 co-precipitation 48.0 — 258 0.64 7.7S4 co-precipitation 20.9 — 304 0.86 7.9 S5 step-precipitation 21.1 — 2390.78 9.4 S6 coating 27.8 — 275 0.48 7.8 S7 coating 18.9 — 271 0.60 8.1S8 coating 43.7 — 229 0.38 5.5 S9 strike-precipitation 23.1 3.2 293 0.566.1 S10 strike-precipitation 21.3 0.5 236 0.56 8.0 S11strike-precipitation 10.8 0.5 240 0.65 9.0 S12 co-extrusion 10.6 0.87247 0.54 6.7 (*) based on the total weight of the support dry base

Catalyst Preparation and Testing Example A: Positive Effect of TiO₂Addition in Different Amounts and Via Different Preparation Methods onthe Activity of NiMo Catalysts

The following examples illustrate the positive effect of TiO₂ additionin the support on the activity of NiMo catalysts when combined withsulfur-containing organics in the catalyst preparation. The catalystswere prepared as described in examples A1-A12 using the same method toapply metals and S-organic additives to the catalysts and have acomparable volume loading of metals in the reactor. The catalysts weretested in a multi-reactor unit under medium pressure ultra-low sulfurdiesel conditions at equal catalyst volume. Table 2 shows thepre-sulfidation and test conditions and Table 3 shows the activityresults.

TABLE 2 Pre-sulfiding and testing (medium P ULSD) format used foractivity testing of NiMo examples A. Pre-sulfiding conditions LHSV PH₂/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) SpikedLGO 3 45 300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed(bar) (Nl/l) (° C.) condition (days) SRGO 1.09 wt. % S 45 300 350 4 and200 ppmN

Example A1: Comparative A1. Comparative A1 was prepared by consecutiveimpregnation of support Comparative A1 with (i) a NiMoP aqueous solutionand, after drying, (ii) with thioglycolic acid. Both impregnations wereperformed in a rotating pan. The metal loaded intermediate was preparedfrom support S1 using impregnation with an amount of aqueous NiMoPsolution equivalent to fill 105% of the pore volume, as is known for aperson skilled in the art. The pore volume of the support was determinedby a so-called water PV measurement in which the point of incipientwetness was determined by addition of water to the carrier extrudates.The NiMoP solution was prepared by dispersing of the required amount ofNiCO₃ in water. The solution was then heated to 60° C. while stirring.Half of the required H₃PO₄ was added carefully to the solution andsubsequently MoO₃ was added in small portions. The solution was heatedup to 92° C. to obtain a clear solution. Finally, the rest of the H₃PO₄was added to the solution and water was added to reach the concentrationrequired for the desired metal loading. After impregnation, theextrudates were allowed to age for 1 hour in a closed vessel, afterwhich drying was carried out at 120° C. for at least one hour.Subsequently, impregnation of the thus formed metal loaded intermediatewith thioglycolic acid was carried out with neat thioglycolic acid toreach a loading of this compound on the catalysts of 3.5 mol/mol metals(Mo+Ni) in the catalyst. The thus formed composite was further aged for2 hour, while rotating. The extrudates were then poured out into a petridish and placed in a static oven at 80° C. for 16 hours. The compositionof the metal impregnated dried catalyst (dry base) was 23.0 wt. % MoO₃,4.5 wt. % NiO, 4.0 wt. % P₂O₅ and the rest is Al₂O₃.

Example A2: Invention A2. Invention A2 was prepared using support S2 andthe same preparation process as in A1. The composition of the metalimpregnated dried catalyst (dry base) was 17.2 wt. % MoO₃ and 3.3 wt. %NiO, 3.1 wt. % P₂O₅, 38.6 wt. % TiO₂ and the rest is Al₂O₃.

Example A3: Invention A3. Invention A3 was prepared using support S3 andthe same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 19.4 wt. % MoO₃ and 3.8 wt. %NiO, 3.5 wt. % P₂O₅, 37.4 wt. % TiO₂ and the rest is Al₂O₃.

Example A4: Invention A4. Invention A4 was prepared using support S4 andthe same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 23.7 wt. % MoO₃ and 4.5 wt. %NiO, 4.1 wt. % P₂O₅, 13.0 wt. % TiO₂ and the rest is Al₂O₃.

Example A5: Invention A5. Invention A5 was prepared using support S5 andthe same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 24.4 wt. % MoO₃ and 4.7 wt. %NiO, 4.3 wt. % P₂O₅, 13.5 wt. % TiO₂ and the rest is Al₂O₃.

Example A6: Invention A6. Invention A6 was prepared using support S6 andthe same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 18.0 wt. % MoO₃ and 3.4 wt. %NiO, 3.1 wt. % P₂O₅, 21.2 wt. % TiO₂ and the rest is Al₂O₃.

Example A7: Invention A7. Invention A7 was prepared using support S7 andthe same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 20.1 wt. % MoO₃ and 4.0 wt. %NiO, 3.5 wt. % P₂O₅, 12.6 wt. % TiO₂ and the rest is Al₂O₃.

Example A8: Invention A8. Invention A8 was prepared using support S8 andthe same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 18.7 wt. % MoO₃ and 3.7 wt. %NiO, 3.4 wt. % P₂O₅, 25.9 wt. % TiO₂ and the rest is Al₂O₃.

Example A9: Invention A9. Invention A9 was prepared using support S9 andthe same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 18.0 wt. % MoO₃ and 3.5 wt. %NiO, 3.3 wt. % P₂O₅, 15.7 wt. % TiO₂ and the rest is Al₂O₃.

Example A10: Comparative A10. Comparative A10 was prepared using supportS1 and the same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 24.8 wt. % MoO₃ and 4.4 wt. %NiO, 4.3 wt. % P₂O₅ and the rest is Al₂O₃.

Example A11: Invention A11. Invention A11 was prepared using support S10and the same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 22.0 wt. % MoO₃ and 3.7 wt. %NiO, 3.8 wt. % P₂O₅, 0.37 wt. % SiO₂, 15.0 TiO₂ wt. % and the rest isAl₂O₃.

Example A12: Invention A12. Invention A12 was prepared using support S11and the same preparation process as A1. The composition of the metalimpregnated dried catalyst (dry base) was 23.6 wt. % MoO₃ and 4.1 wt. %NiO, 4.0 wt. % P₂O₅, 0.36 wt. % SiO₂, 7.4 wt. % TiO₂ and the rest isAl₂O₃.

TABLE 3 The effect of the addition of TiO₂ in combination with a sulfurcontaining organic on the activity of supported NiMo catalysts in mediumP ULSD activity testing. RVA RVA g_(CAT) db mg MoO₃ LHSV N HDN LHSV SHDS Example Support Reactor Reactor HDN (ppm) r.o. 1.0 HDS (ppm) r.o.1.2 Comparative A1 S1 0.720 184 4.0 49 100% 2.5 151 100% Invention A2 S20.881 168 40 108% 99 113% Invention A3 S3 0.794 171 22 152% 42 151%Invention A4 S4 0.647 170 44 105% 119 107% Invention A5 S5 0.640 173 35123% 65 130% Invention A6 S6 0.990 189  9 211% 24 170% Invention A7 S70.844 184 19 165% 33 169% Invention A8 S8 0.936 195 11 197% 28 171%Invention A9 S9 0.856 171 17 175% 38 155% Comparative A10 S1 0.719 19858 100% 2.7 144 100% Invention A11 S10 0.855 209  9 246% 24 177%Invention A12 S11 0.820 215 19 190% 29 169%

As can be seen in Table 3, the catalysts that were prepared using aTi-containing support are significantly more active in HDN and HDS thanthe comparative catalyst without any Ti (A1, A10) using the sameS-containing organic additive, impregnation method and amount of metalsin the reactor. Since different LHSV have been used, RVAs of InventionsA2-A9 are relative to the activity of Comparative A1 and RVAs ofInventions A11-A12 are relative to Comparative A10.

Examples B: Positive Effect of TiO₂ Addition in Different Amounts andVia Different Preparation Methods on the Activity of CoMo Catalysts

These examples illustrate the positive effect of addition of TiO₂ in thesupport on the activity of CoMo catalysts when combined withsulfur-containing organics in the preparation in a wide range of TiO₂contents. Catalysts B1-B10 were all prepared using the same method toapply metals and thioglycolic acid to the catalyst and have a comparablevolume loading of metals in the reactor. The catalysts were tested in amulti-reactor unit under medium pressure ultra-low sulfur dieselconditions. Table 4 shows the pre-sulfidation and Table 5 shows theactivity results.

TABLE 4 Pre-sulfiding and testing (medium P ULSD) format used foractivity testing of CoMo examples B. Pre-sulfiding conditions LHSV PH₂/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) SpikedLGO 3 45 300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed(bar) (Nl/l) (° C.) condition (days) SRGO 1.09 wt. % S 45 300 350 4 and200 ppmN

Example B1: Comparative B1. Comparative B1 was prepared by consecutiveimpregnation of support Comparative A1 with (i) a CoMoP aqueous solutionand, after drying, (ii) with thioglycolic acid. Both impregnations wereperformed in a rotating pan. The metal loaded intermediate was preparedfrom support S1 using impregnation with an amount of aqueous CoMoPsolution equivalent to fill 105% of the pore volume, as is known for aperson skilled in the art. The pore volume of the support was determinedby a so-called water PV measurement in which the point of incipientwetness was determined by addition of water to the carrier extrudates.The CoMoP solution was prepared by dispersing of the required amount ofCoCO₃ in water. The solution was then heated to 60° C. while stirring.Half of the required H₃PO₄ was added carefully to the solution andsubsequently MoO₃ was added in small portions. The solution was heatedup to 92° C. to obtain a clear solution. Finally, the rest of the H₃PO₄was added to the solution and water was added to reach the concentrationrequired for the desired metal loading. After impregnation, theextrudates were allowed to age for 1 hour in a closed vessel, afterwhich drying was carried out at 120° C. for at least one hour.Subsequently, impregnation of the thus formed metal loaded intermediatewith thioglycolic acid was carried out with neat thioglycolic acid toreach a loading of this compound on the catalysts of 3.5 mol/mol metals(Mo+Co) in the catalyst. The thus formed composite was further aged for2 hours, while rotating. The extrudates were then poured out into apetri dish and placed in a static oven at 80° C. for 16 hours. Thecomposition of the metal impregnated dried catalyst (dry base) was 24.0wt. % MoO₃ and 4.6 wt. % CoO, 4.2 wt. % P₂O₅ and the rest is Al₂O₃.

Example B2: Invention B2. Invention B2 was prepared using support S3 andthe same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 19.1 wt. % MoO₃ and 3.6 wt. %CoO, 3.3 wt. % P₂O₅, 37.2 wt. % TiO₂ and the rest is Al₂O₃.

Example B3: Invention B3. Invention B3 was prepared using support S5 andthe same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 19.8 wt. % MoO₃ and 3.8 wt. %CoO, 3.3 wt. % P₂O₅, 12.4 wt. % TiO₂ and the rest is Al₂O₃.

Example B4: Inventive B4. Invention B4 was prepared using support S6 andthe same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 19.1 wt. % MoO₃ and 3.6 wt. %CoO, 3.3 wt. % P₂O₅, 20.7 wt. % TiO₂ and the rest is

Example B5: Invention B5. Invention B5 was prepared using support S7 andthe same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 19.8 wt. % MoO₃ and 3.8 wt. %CoO, 3.5 wt. % P₂O₅, 20.1 wt. % TiO₂ and the rest is Al₂O₃.

Example B6: Comparative B6. Comparative B6 was prepared using support S1and the same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 26.5 wt. % MoO₃ and 4.8 wt. %CoO, 4.4 wt. % P₂O₅ and the rest is Al₂O₃.

Example B7: Invention B7. Invention B7 was prepared using support S9 andthe same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 24.2 wt. % MoO₃ and 4.5 wt. %CoO, 4.1 wt. % P₂O₅, 1.8 wt. % SiO₂, 13.9 wt. % TiO₂ and the rest isAl₂O₃.

Example B8: Comparative B8. Comparative B8 was prepared using support S1and the same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 26.1 wt. % MoO₃ and 4.8 wt. %CoO, 4.4 wt. % P₂O₅ and the rest is Al₂O₃.

Example B9: Invention B9. Invention B9 was prepared using support S10and the same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 23.4 wt. % MoO₃ and 3.9 wt. %CoO, 4.0 wt. % P₂O₅, 0.36 wt. % SiO₂, 14.7 wt. % TiO₂ and the rest isAl₂O₃.

Example B10: Invention B10. Invention B10 was prepared using support S11and the same preparation process as B1. The composition of the metalimpregnated dried catalyst (dry base) was 20.5 wt. % MoO₃ and 4.3 wt. %CoO, 4.3 wt. % P₂O₅, 0.36 wt %. SiO₂, 7.2 wt. % TiO₂ and the rest isAl₂O₃.

TABLE 5 The effect of the addition of a sulfur containing organic incombination with TiO₂-containing support in the activity of CoMocatalysts in medium P ULSD activity testing. g_(CAT) db mg MoO₃ LHSV NRVA HDN Example Support Reactor Reactor HDN (ppm) r.o. 1 Comparative B1S1 0.730 194 3.5 50 100% Invention B2 S3 0.837 180 26 158% Invention B3S5 0.829 182 34 131% Invention B4 S6 0.919 187 21 160% Invention B5 S70.891 196 20 174% Comparative B6 S1 0.731 215 3.2 34 100% Invention B7S9 0.789 212  4 224% Comparative B8 S1 0.701 203 4.0 88 100% InventionB9 S10 0.893 232 19 259% Invention B10 S11 0.812 226 40 186%

As can be seen in Table 5, the catalysts that were prepared on aTi-containing supports (B2-B5, B7 and B9-B10) are significantly moreactive in HDN than the comparative catalysts without any Ti (B1, B6 andB8) using the same S-organic additive and impregnation method. Sincedifferent LHSV have been used, RVAs of Inventions B2-B5 are relative tothe activity of Comparative B1, RVA of Inventions B7 is relative toComparative B6 and RVAs of Inventions B9-B10 are relative to ComparativeB8.

Examples C: Positive effect of a wide variation of S-organic additiveson the activity of NiMo and CoMo catalysts

These examples illustrate the positive effect of S-organic additives onthe activity of NiMo and CoMo catalysts when combined withTiO₂-containing. The catalyst examples are 4 NiMo and 4 CoMo gradesbased on the same Ti—Al support and different sulfur-organic additives.They were prepared using the same method to apply metals and have acomparable volume loading of metals in the reactor. The catalysts weretested in a multi-reactor unit under medium pressure ultra-low sulfurdiesel conditions. Table 6 shows the pre-sulfidation and test conditionsused for both NiMo and CoMo catalysts and Table 7 and 8 shows theactivity results.

TABLE 6 Pre-sulfiding and testing (medium P ULSD) format used foractivity testing of NiMo and CoMo catalysts from examples C.Pre-sulfiding conditions LHSV P H₂/oil Temperature Time Feed (1/hr)(bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testingconditions P H₂/oil Temperature Time @ Feed (bar) (Nl/l) (° C.)condition (days) SRGO 1.09 wt. % 45 300 350 4 and 200 ppmN

Example C1: Comparative C1. Comparative C1 was prepared by impregnationof a NiMoP aqueous solution (no S-organic additive) on support S11. Theimpregnation was performed in a rotating pan with an amount of aqueousNiMoP solution equivalent to fill 105% of the pore volume, as is knownfor a person skilled in the art. The pore volume of the support wasdetermined by a so-called water PV measurement in which the point ofincipient wetness was determined by addition of water to the carrierextrudates. The NiMoP solution was prepared by dispersing of therequired amount of NiCO₃ in water. The solution was then heated to 60°C. while stirring. Half of the required H₃PO₄ was added carefully to thesolution and subsequently MoO₃ was added in small portions. The solutionwas heated up to 92° C. to obtain a clear solution. Finally, the rest ofthe H₃PO₄ was added to the solution and water was added to reach theconcentration required for the desired metal loading. Afterimpregnation, the extrudates were allowed to age for 1 hour in a closedvessel, after which drying was carried out at 120° C. for at least onehour. The extrudates were then poured out into a petri dish and placedin a static oven at 80° C. for 16 hours. The composition of the metalimpregnated dried catalyst (dry base) was 23.6 wt. % MoO₃ and 4.1 wt. %NiO, 4.0 wt. % P₂O₅, 0.36 wt. % SiO₂, 7.4 wt. % TiO₂ and the rest isAl₂O₃.

Example C2: Invention C2. Invention C2 was prepared using ComparativeC1. A second impregnation with thiolactic acid at 95% PV saturation wasperformed without the use of H₂O, and aged for 2 hours at 80° C. Theextrudates were then poured out into a petri dish and placed in a staticoven at 80° C. for 16 hours. The composition of the metal impregnateddried catalyst (dry base) was the same as Comparative C1.

Example C3: Invention C3. Invention C3 was prepared using ComparativeC1. A second impregnation with 3-mercaptopropionic acid was performedwith a fixed amount reaching 15 wt. % carbon of the total catalyst, andaged for 2 hour at 80° C. The extrudates were then poured out into apetri dish and placed in a static oven at 80° C. for 16 hours. Thecomposition of the metal impregnated dried catalyst (dry base) was thesame as Comparative C1.

Example C4: Invention C4. Invention C4 was prepared Comparative C1. Asecond impregnation with mercaptosuccinic acid was performed with afixed amount reaching 15 wt. % carbon of the total catalyst, and agedfor 2 hours at 80° C. The extrudates were then poured out into a petridish and placed in a static oven at 80° C. for 16 hours. The compositionof the metal impregnated dried catalyst (dry base) was the same asComparative C1.

TABLE 7 The effect of the addition of a sulfur-containing organic incombination with TiO₂- containing support in the activity of NiMocatalysts in medium P ULSD activity testing. g_(CAT) db mg MoO₃ LHSV NRVA HDN LHSV S RVA HDS Example Support Reactor Reactor HDN (ppm) r.o. 1HDS (ppm) r.o. 1.2 Comparative C1 S11 0.787 206 4.0 66 100% 2.7 175 100%Invention C2 S11 0.770 202 40 153%  65 147% Invention C3 S11 0.768 20156 116% 104 120% Invention C4 S11 0.780 205 46 124%  74 128%

As observed in Table 7, the NiMo catalysts with different types ofS-containing organic additives (C2-C4) show higher HDN and HDSactivities than the comparative (C1) example without organic additivesusing the same support (S11) and similar metal loadings (ca. 200gMoO₃/Reactor).

Example C5: Comparative C5. Comparative C5 was prepared from support S11using impregnation with an amount of aqueous CoMoP solution equivalentto fill 105% of the pore volume, as is known for a person skilled in theart. The CoMoP solution was prepared by dispersing of the requiredamount of CoCO₃ in water. The solution was then heated to 60° C. whilestirring. Half of the required H₃PO₄ was added carefully to the solutionand subsequently MoO₃ was added in small portions. The solution washeated up to 92° C. to obtain a clear solution. Finally, the rest of theH₃PO₄ was added to the solution and water was added to reach theconcentration required for the desired metal loading. Afterimpregnation, the extrudates were allowed to age for 1 hour in a closedvessel, after which drying was carried out at 120° C. for at least onehour. The extrudates were then poured out into a petri dish and placedin a static oven at 80° C. for 16 hours. The composition of the metalimpregnated dried catalyst (dry base) was 23.2 wt. % MoO₃, 3.9 wt. %CoO, 2.4 wt. % P₂O₅, 0.37 wt. % SiO₂, 7.5 wt. % TiO₂ and the rest isAl₂O₃.

Example C6: Invention C6. Invention C6 was prepared using ComparativeC5. A second impregnation with thiolactic acid at 95% PV saturation wasperformed without the use of H₂O, and aged for 2 hours at 80° C. Theextrudates were then poured out into a petri dish and placed in a staticoven at 80° C. for 16 hours. The composition of the metal impregnateddried catalyst (dry base) was the same as Comparative C5.

Example C7: Invention C7. Invention C7 was prepared using ComparativeC5. A second impregnation with 3-mercaptopropionic acid was performedwith a fixed amount reaching 15 wt. % carbon of the total dried basecatalyst, and aged for 2 hours at 80° C. The extrudates were then pouredout into a petri dish and placed in a static oven at 80° C. for 16hours. The composition of the metal impregnated dried catalyst (drybase) was the same as Comparative C5.

Example C8: Invention C8. Invention C8 was prepared using ComparativeC5. A second impregnation with mercaptosuccinic acid was performed witha fixed amount reaching 15 wt. % carbon of the total dried basecatalyst, and aged for 2 hours at 80° C. The extrudates were then pouredout into a petri dish and placed in a static oven at 80° C. for 16hours. The composition of the metal impregnated dried catalyst (drybase) was the same as Comparative C5.

TABLE 8 The effect of the addition of a sulfur-containing organic incombination with TiO₂- containing support in the activity of CoMocatalysts in medium P ULSD activity testing. g_(CAT) mg RVA db MoO₃ LHSVN HDN Example Support Reactor Reactor HDN (ppm) r.o. 1 Comparative C5S11 0.77 197 4.0 89 100% Invention C6 S11 0.79 203 52 158% Invention C7S11 0.8 223 63 137% Invention C8 S11 0.77 197 74 116%

As observed in Table 8, the CoMo catalysts with different types ofS-containing organic additives (C6-C8) show higher HDN activity than thecomparative (C5) example without organic additives using the samesupport (S11) and similar metal loadings (ca. 200 gMoO₃/Reactor).

Examples D: The Synergetic Effect of Sulfur-Containing Organics &Ti—Al₂O₃ Support for NiMo Catalysts

In the following examples, it is illustrated that the use of aTiO₂/Al₂O₃ support in combination with S-organics results in asynergetic effect for NiMo catalysts. The activity benefit of applying aTiO₂/Al₂O₃ support in combination with S-organics is higher than can beexpected based on the separate contributions of the (i) TiO₂/Al₂O₃support and (ii) the S-organics as determined in separate experimentsand can therefore be regarded as surprising. The NiMo catalyst examplespresented have comparable metal loadings and were tested in amulti-reactor unit under medium pressure ultra-low sulfur dieselconditions. Table 9 shows the experimental settings for thepre-sulfidation and test conditions and Table 10 shows the amount ofcatalyst that was loaded in the different reactors and the activityresults.

TABLE 9 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of NiMo catalysts from examples D. Pre-sulfiding conditions LHSVP H₂/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) SpikedLGO 3 45 300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed(bar) (Nl/l) (° C.) condition (days) SRGO 1.09 wt. % 45 300 350 4 and200 ppmN

Example D1: Comparative D1. Comparative D1 was prepared using support S1and impregnated with NiMoP aqueous solution and no organic additive. Themethod used for preparation of the impregnation solution is the same asthe method described in Example C1. The composition of the metalimpregnated dried catalyst (dry base) was 24.8 wt. % MoO₃, 4.2 wt. %NiO, 2.7 wt. % P₂O₅ and the rest Al₂O₃.

Example D2: Comparative D2. Comparative D2 was prepared using support S1and impregnated with NiMoP aqueous solution and thioglycolic acidadditive. The method used for preparation of the impregnation solution,and the amount of S-organics applied (relative to the metals) is thesame as the method described in Example A1. The composition of the metalimpregnated dried catalyst (dry base) was the same as D1.

Example D3: Comparative D3. Comparative D3 was prepared using supportS10 and impregnated with NiMoP aqueous solution and no organic additive.The method used for preparation of the impregnation solution is the sameas the method described in Example C1. The composition of the metalimpregnated dried catalyst (dry base) was 21.8 wt. % MoO₃, 3.6 wt. %NiO, 2.4 wt. % P₂O₅, 0.38 wt. % SiO₂, 15.4 wt. % TiO₂ and the restAl₂O₃.

Example D4: Invention D4. Invention D4 was prepared using support S10and impregnated with NiMoP aqueous solution and thioglycolic acidadditive. The method used for preparation of the impregnation solution,and the amount of S-organics applied (relative to the metals) is thesame as the method described in Example A1. The composition of the metalimpregnated dried catalyst (dry base) was the same as Example D3.

Example D5: Comparative D5. Comparative D5 was prepared using supportS11 and impregnated with NiMoP aqueous solution and no organic additive.The method used for preparation of the impregnation solution is the sameas the method described in Example C1.

The composition of the metal impregnated dried catalyst (dry base) was23.3 wt. % MoO₃, 3.7 wt. % NiO, 2.5 wt. % P₂O₅, 0.38 wt. % SiO₂, 7.6 wt.% TiO₂ and the rest Al₂O₃.

Example D6: Invention D6. Invention D6 was prepared using support S11and impregnated with NiMoP aqueous solution and thioglycolic acidadditive. The method used for preparation of the impregnation solution,and the amount of S-organics applied (relative to the metals) is thesame as the method described in Example A1. The composition of the metalimpregnated dried catalyst (dry base) was the same as Example D5.

TABLE 10 The effect of the addition of a sulfur containing organic incombination with TiO₂-containing support in the activity of NiMocatalysts in medium P ULSD activity testing. RVA mg RVA HDS g_(CAT) dbMoO₃ LHSV N HDN Sxy LHSV S r.o. Sxy Example Support Reactor Reactor HDN(ppm) r.o. 1 HDN HDS (ppm) 1.2 HDS Comparative D1 S1 0.710 196 4.0 87100% 2.7 261 100% Comparative D2 S1 0.713 197 67 121% 183 110%Comparative D3 S10 0.829 201 53 141%  94 135% Invention D4 S10 0.847 205 6 370% 208  20 221% 76 Comparative D5 S11 0.762 197 73 114% 211 106%Invention D6 S11 0.793 205 23 218%  83  29 192% 76

As observed in Table 10, the activity benefit of the catalysts of theinvention (D4 and D6), containing TiO₂ in the support and S-containingorganics are larger than expected from the individual benefits oftitania addition (D3 and D5, without S-organic additive) or use ofS-organic additive (D2, without titania). Both inventions are ultimatelycompared with Comparative D1 (no organic and no titania) at similarmetal loadings.

To determine the extent of the synergy between the effect of (i) TiO₂addition to the support and (ii) addition of S-containing organics oncatalyst activity, we determined Synergy factor Sxy as defined inEquation 1. RVA_(0,0) is the relative activity of the reference catalyst(without Ti (x) or organics (y)) Values for ax and by were determinedfrom the RVA of the comparative catalyst that is based on the Al₂O₃support with the same organics (RVA_(x,0)=RVA_(0,0)+ax) and the RVA ofthe comparative catalyst based on the TiO₂—Al₂O₃ support withoutorganics (RVA_(0,y)=RVA_(0,0)+by). A positive value of Sxy signifiesthat the activity of catalysts of the invention is higher than could beexpected based on the individual contributions of the support and theorganics on catalyst activity.

RVA _(x,y) =RVA _(0,0) +ax+by+Sxy  [Eq. 1]

Examples E: The Synergetic Effect of Sulfur-Containing Organics &Ti—Al₂O₃ Support for CoMo Catalysts

In the following examples, it is illustrated that the use of aTiO₂/Al₂O₃ support in combination with S-organics results in asynergetic effect for CoMo catalysts for a wide range of metal loadings.The activity benefit of applying a TiO₂/Al₂O₃ support in combinationwith S-organics is higher than can be expected based on the separatecontributions of the (i) TiO₂/Al₂O₃ support and (ii) the S-organics asdetermined in separate experiments and can therefore be regarded assurprising. The CoMo catalyst examples presented have been tested in amulti-reactor unit under medium pressure ultra-low sulfur dieselconditions. The set of examples have been tested at a comparablevolumetric metal loading. A first set at high metal loading (ExamplesE1-E4) and a second set at low metal loading (Examples E5-E8). Tables 11and 13 show the experimental settings for the pre-sulfidation and testconditions and Tables 12 and 14 show the amount of catalyst that wasloaded in the different reactors and the activity results.

Example E1: Comparative E1. Comparative E1 was prepared using support S1and impregnated with CoMoP aqueous solution and no organic additive. Themethod used for preparation of the impregnation solution is the same asthe method described in Example C5. The composition of the metalimpregnated dried catalyst (dry base) was 24.6 wt. % MoO₃, 4.3 wt. %CoO, 2.6 wt. % P₂O₅ and the rest Al₂O₃.

Example E2: Comparative E2. Comparative E2 was prepared using support S1and impregnated with CoMoP aqueous solution and thioglycolic acidadditive. The method used for preparation of the impregnation solutionis the same as the method described in Example B1. The composition ofthe metal impregnated dried catalyst (dry base) was the same as E1.

Example E3: Comparative E3. Comparative E3 was prepared using supportS11 and impregnated as the method described in Example E1. Thecomposition of the metal impregnated dried catalyst (dry base) was 21.8wt. % MoO₃, 3.7 wt. % CoO, 2.3 wt. % P₂O₅, 0.38 wt. % SiO₂, 15.2 wt. %TiO₂ and the rest Al₂O₃.

Example E4: Invention E4. Invention E4 was prepared using support S11and impregnated as the method described in Example E1. The compositionof the metal impregnated dried catalyst (dry base) was the same asExample E3.

TABLE 11 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of the high metal loading CoMo catalysts from examples E.Pre-sulfiding conditions LHSV P H₂/oil Temperature Time Feed (1/hr)(bar) (Nl/l) (° C.) (hours) Spiked LGO 3 45 300 320 24 Testingconditions P H₂/oil Temperature Time @ Feed (bar) (Nl/l) (° C.)condition (days) SRGO 1.09 wt. % 45 300 350 4 and 200 ppmN

TABLE 12 The effect of the addition of a sulfur containing organic incombination with TiO₂-containing support in the activity of high metalloading CoMo catalysts in medium P ULSD activity testing. g_(CAT) db mgMoO₃ LHSV N RVA HDN Sxy Example Support Reactor Reactor HDN (ppm) r.o. 1HDN Comparative E1 S1 0.682 186 4.0 100 100% Comparative E2 S1 0.701 192 81 132% Comparative E3 S10 0.829 201  67 145% Invention E4 S10 0.83 201 37 226% 49

As observed in Table 12, the activity benefit of the invention (E4) islarger than expected from the individual benefits of titania addition(E3, without S-organic additive) or use of S-organic additive (E2,without titania). The activity of all catalysts is ultimately comparedwith Comparative E1 (no organic and no titania) at similar metalloadings.

Example E5: Comparative E5. Comparative E5 was prepared using support S1and impregnated, as E1, with CoMoP aqueous solution without organics.The composition of the metal impregnated dried catalyst (dry base) was19.3 wt. % MoO₃ and 3.6 wt. % CoO, 3.2 P₂O₅ wt. % and the rest is Al₂O₃.

Example E6: Comparative E6. Comparative E6 was prepared using support S9and impregnated as E5. The composition of the metal impregnated driedcatalyst (dry base) was 17.5 wt. % MoO₃ and 3.2 wt. % CoO, 2.9 P₂O₅ wt.%, 15.8 TiO₂ wt. %, 2.0 SiO₂ wt. % and the rest is Al₂O₃.

Example E7: Comparative E7. Comparative E7 was prepared using supportS1. Firstly, it was impregnated with CoMoP aqueous solution as E1 andafter drying a second impregnation with thioglycolic acid (3.5 mol/molmetals in the catalyst) in a rotating pan was performed. Theintermediate was further aged for 2 hour, while rotating, and thenpoured out into a petri dish and placed in a static oven at 80° C. for16 hours. The composition of the metal impregnated dried catalyst (drybase) was 19.3 wt. % MoO₃ and 3.6 wt. % CoO, 3.2 P₂O₅ wt. % and the restis Al₂O₃.

Example E8: Invention E8. Invention E8 was prepared using support S9 andimpregnated as E7. The composition of the metal impregnated driedcatalyst (dry base) was 17.5 wt. % MoO₃ and 3.2 wt. % CoO, 2.9 P₂O₅ wt.%, 15.7 TiO₂ wt. % and 2.1 SiO₂ wt. %.

TABLE 13 Pre-sulfiding and test (medium P ULSD) format used for activitytesting of low metal loading CoMo examples E. Pre-sulfiding conditionsLHSV P H₂/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours)Spiked LGO 3 45 300 320 24 Testing conditions P H₂/oil Temperature Time@ Feed (bar) (Nl/l) (° C.) condition (days) SRGO 1.4 wt. % S 45 300 3503 and 200 ppmN

TABLE 14 The effect of the addition of an organic in combination withTiO₂-containing support in the activity of CoMo catalysts low metalloading in medium P ULSD activity testing. Mg RVA RVA g_(CAT) db MoO₃LHSV N HDN Sxy LHSV S HDS Sxy Example Support Reactor Reactor HDN (ppm)r.o. 1 HDN HDS (ppm) r.o. 1.2 HDS Comparative E5 S1 0.634 136 2.6 86100% 2.0 244 100% Comparative E6 S9 0.736 143 2.6 38 192% 119 126%Comparative E7 S1 0.611 131 2.8 68 129% 143 108% Invention E8 S9 0.714139 2.8  7 362% 141  24 172% 38 CoMo commercial catalyst 0.731 196 2.627 235%  50 161% CoMo commercial catalyst 0.742 196 2.8 28 235%  41 161%

In the case of low metal loading catalysts a synergetic effect betweenthe support and the organics is also observed. This was surprising sinceneither TiO₂ nor the organics applied in the preparation will contributedirectly to the activity of the catalysts. This effect can be clearlyobserved for a wide range of metal loadings (high ca. 220 gMoO₃/L andlow around 140 gMoO₃/L) and most easily observed in the HDN activities.Finally, the activity of the low metal loading catalyst of the invention(E8) can be compared to that of a CoMo commercial catalyst that wasincluded in the same test.

Examples F: The Benefit of TiO₂—Al₂O₃ Co-Extruded Support in Combinationwith S-Organic Additives for NiMo Catalysts in HC-PT Application

The following examples illustrate the positive effect of TiO₂ additionin the support on the activity of NiMo catalysts when combined withS-containing organics in the catalyst preparation. The catalysts wereprepared as described in examples F1-F2 using the same method to applymetals to the catalysts and have a comparable volume loading of metalsin the reactor. The catalysts were tested in a multi-reactor unit HC-PTconditions. Table 15 shows the pre-sulfidation and test conditions andTable 16 shows the activity results.

TABLE 15 Pre-sulfiding and test (HC-PT) format used for activity testingof low metal loading NiMo examples F. Pre-sulfiding conditions LHSV PH₂/oil Temperature Time Feed (1/hr) (bar) (Nl/l) (° C.) (hours) SpikedLGO 3 45 300 320 24 Testing conditions P H₂/oil Temperature Time @ Feed(bar) (Nl/l) (° C.) condition (days) VGO 2.1 wt. % S 120 1000 380 3 and1760 ppmN

Example F1: Comparative F1. Comparative F1 was prepared using support S1and a NiMoP aqueous solution. The catalyst was prepared from support S1impregnated with an amount of aqueous NiMoP solution equivalent to fill105% of the pore volume, as is known for a person skilled in the art.The pore volume of the support was determined by a so-called water PVmeasurement in which the point of incipient wetness was determined byaddition of water to the carrier extrudates. The NiMoP solution wasprepared by dispersing of the required amount of NiCO₃ in water. Thesolution was then heated to 60° C. while stirring. Half of the requiredH₃PO₄ was added carefully to the solution and subsequently MoO₃ wasadded in small portions. The solution was heated up to 92° C. to obtaina clear solution. Finally, the rest of the H₃PO₄ was added to thesolution and water was added to reach the concentration required for thedesired metal loading. After impregnation, the extrudates were allowedto age for 1 hour in a closed vessel, after which drying was carried outat 120° C. for at least one hour. The extrudates were then poured outinto a petri dish and placed in a static oven at 80° C. for 16 hours.The composition of the metal impregnated dried catalyst (dry base) was25.9 wt. % MoO₃, 4.1 wt. % NiO, 4.4 wt. % P₂O₅ and the rest is Al₂O₃.

Example F2: Invention F2. Invention F2 was prepared using support S12and impregnated with an amount of aqueous NiMoP solution equivalent tofill 105% of the pore volume, as is known for a person skilled in theart. The pore volume of the support was determined by a so-called waterPV measurement in which the point of incipient wetness was determined byaddition of water to the carrier extrudates. The NiMoP solution wasprepared by dispersing of the required amount of NiCO₃ in water. Thesolution was then heated to 60° C. while stirring. Half of the requiredH₃PO₄ was added carefully to the solution and subsequently MoO₃ wasadded in small portions. The solution was heated up to 92° C. to obtaina clear solution. Finally, the rest of the H₃PO₄ was added to thesolution and water was added to reach the concentration required for thedesired metal loading. After impregnation, the extrudates were allowedto age for 1 hour in a closed vessel, after which drying was carried outat 120° C. for at least one hour. The extrudates were then poured outinto a petri dish and placed in a static oven at 80° C. for 16 hours.Subsequently, impregnation of the thus formed metal loaded intermediatewith thioglycolic acid was carried out with neat thioglycolic acid toreach a loading of this compound on the catalysts of 3.5 mol/mol metals(Mo+Ni) in the catalyst. The thus formed composite was further aged for2 hours, while rotating. The composition of the metal impregnated driedcatalyst (dry base) was 24.1 wt. % MoO₃, 4.0 wt. % NiO, 4.1 P₂O₅ wt. %,7.2 wt. % TiO₂, 0.59 wt. % SiO₂ and the rest is Al₂O₃.

TABLE 16 The effect of the addition of an organic in combination withTiO₂-containing support in the activity of NiMo catalysts in HC-PTactivity testing. g_(CAT) Mg RVA db MoO₃ LHSV N HDN Example SupportReactor Reactor HDN (ppm) r.o. 1 Comparative F1 S1 0.719 186 1.70 182100 Invention F2 S12 0.940 226  57 156

As can be observed in table 16, Invention F2 containing S-organicadditives and titanium in the support show higher benefits in both HDNand HDS than the Comparative F1 example. The benefit of combining aS-organic additive and a Ti-containing support is visible also for HC-PTapplications.

Components referred to by chemical name or formula anywhere in thespecification or claims hereof, whether referred to in the singular orplural, are identified as they exist prior to coming into contact withanother substance referred to by chemical name or chemical type (e.g.,another component, a solvent, or etc.). It matters not what chemicalchanges, transformations and/or reactions, if any, take place in theresulting mixture or solution as such changes, transformations, and/orreactions are the natural result of bringing the specified componentstogether under the conditions called for pursuant to this disclosure.Thus the components are identified as ingredients to be brought togetherin connection with performing a desired operation or in forming adesired composition.

The invention may comprise, consist, or consist essentially of thematerials and/or procedures recited herein.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions of the invention or employed in the methods of theinvention refers to variation in the numerical quantity that can occur,for example, through typical measuring and liquid handling proceduresused for making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. The term “about”also encompasses amounts that differ due to different equilibriumconditions for a composition resulting from a particular initialmixture. Whether or not modified by the term “about”, the claims includeequivalents to the quantities.

Except as may be expressly otherwise indicated, the article “a” or “an”if and as used herein is not intended to limit, and should not beconstrued as limiting, the description or a claim to a single element towhich the article refers. Rather, the article “a” or “an” if and as usedherein is intended to cover one or more such elements, unless the textexpressly indicates otherwise.

Each and every patent or other publication or published documentreferred to in any portion of this specification is incorporated in totointo this disclosure by reference, as if fully set forth herein.

This invention is susceptible to considerable variation in its practice.Therefore the foregoing description is not intended to limit, and shouldnot be construed as limiting, the invention to the particularexemplifications presented hereinabove.

1. A catalyst comprising at least one Group VIB metal component, atleast one Group VIII metal component, at least one sulfur containingorganic additive component, and a titanium-containing carrier component,wherein the amount of titanium content is in the range of about 1 toabout 60 wt %, expressed as an oxide (TiO₂), based on the total weightof the catalyst.
 2. The catalyst of claim 1 wherein the Group VIB metalcomponent is in an amount of about 15 to about 30 wt % expressed as anoxide based on the total weight of the catalyst.
 3. The catalyst ofclaim 1 wherein the Group VIII metal component is in an amount of about2 to about 8 wt % expressed as an oxide based on the total weight of thecatalyst.
 4. The catalyst according to claim 1 wherein the Group VIBmetal component comprises molybdenum and/or tungsten.
 5. The catalystaccording to claim 1 wherein the Group VIII metal component comprisesnickel and/or cobalt.
 6. The catalyst of claim 1 wherein the at leastone sulfur containing organic component comprises a mercapto carboxylicacid.
 7. The catalyst of claim 6 wherein the mercapto carboxylic acid isthioglycolic acid, thiolactic acid, thiopropionic acid, mercaptosuccinic acid or cysteine.
 8. The catalyst of claim 1 further comprisinga phosphorous component in the amount of about 1 to about 8% expressedas oxide based on the total weight of the catalyst.
 9. The catalyst ofclaim 1 wherein the at least one sulfur containing organic additivecomponent is in amount of about 1 to about 30 wt % C.
 10. The catalystof claim 9 wherein the at least one sulfur containing organic additivecomponent is in amount of about 1 to about 20 wt % C.
 11. The catalystof claim 10 wherein the at least one sulfur containing organic additivecomponent is in amount of about 5 to about 15 wt % C.
 12. A method ofproducing a catalyst, the method comprising co-extruding a titaniumsource with a porous material comprising Al₂O₃ to form atitanium-containing carrier extrudate, drying and calcining theextrudate, and impregnating the calcined extrudate with a sulfurcontaining organic additive, at least one Group VIB metal source and/orat least one Group VIII metal source, the amount of the titanium sourcebeing sufficient so as to form a catalyst composition at least having atitanium content in the range of about 1 wt % to about 60 wt %,expressed as an oxide (TiO₂), based on the total weight of the catalyst.13. A method of producing a catalyst, the method comprisingprecipitating a titanium source with an aluminum source, extruding theprecipitate to form a titanium-containing carrier extrudate, drying andcalcining the extrudate, and impregnating the calcined extrudate with asulfur containing organic additive, at least one Group VIB metal sourceand/or at least one Group VIII metal source, the amount of the titaniumsource being sufficient so as to form a catalyst composition at leasthaving a titanium content in the range of about 1 wt % to about 60 wt %,expressed as an oxide (TiO₂), based on the total weight of the catalyst.14. The method of claim 13 wherein the precipitation comprises the stepsof (a) simultaneous dosing of sodium aluminate and aluminum sulfate towater at a fixed pH (b) the formed alumina filter cake is re-slurried inwater (c) to this slurry TiOSO₄ or titanium sulfate is added at a fixedpH>7 controlled by an alkaline solution.
 15. The method of claim 13wherein the aluminum source and the titanium source are mixed in onestream and sodium aluminate is dosed either simultaneously orsubsequently to water at a pH>7.
 16. A method of producing a catalyst,the method comprising impregnating a porous material comprising Al₂O₃with a titanium source to form a titanium-containing carrier, drying andcalcining the carrier, and impregnating the calcined carrier with asulfur containing organic additive, at least one Group VIB metal sourceand/or at least one Group VIII metal source, the amount of the titaniumsource being sufficient so as to form a catalyst composition at leasthaving a titanium content in the range of about 1 wt % to about 60 wt %,expressed as an oxide (TiO₂), based on the total weight of the catalyst.17. The method of claim 12, 13 or 16 further comprising the impregnationwith a sulfur containing organic additive, at least one Group VIB metalsource and/or at least one Group VIII metal source being performed in asingle step with a solution comprising a sulfur containing organicadditive, at least one Group VIB metal source and/or at least one GroupVIII metal source.
 18. The method of claim 12, 13 or 16 furthercomprising the impregnation with a sulfur containing organic additive,at least one Group VIB metal source and/or at least one Group VIII metalsource being performed in more than one step, wherein the carrier isimpregnated with a solution comprising at least one Group VIB metalsource and/or at least one Group VIII metal source, followed by a stepof impregnating the carrier with a solution comprising a sulfurcontaining organic additive.
 19. The method of claim 12, 13 or 16wherein the titanium source is selected from the group consisting oftitanyl sulfate, titanium sulfate, titanium alkoxide orTitanium(IV)bis(ammonium lactato)dihydroxide.
 20. A method whichcomprises contacting a hydrocarbon feed with a catalyst according to anyof the preceding claims, under hydrotreating conditions so as tohydrotreat the hydrocarbon feed.